CN101678322B - Process for producing catalyst support for exhaust gas purification and catalyst support for exhaust gas purification - Google Patents
Process for producing catalyst support for exhaust gas purification and catalyst support for exhaust gas purification Download PDFInfo
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- CN101678322B CN101678322B CN2008800164165A CN200880016416A CN101678322B CN 101678322 B CN101678322 B CN 101678322B CN 2008800164165 A CN2008800164165 A CN 2008800164165A CN 200880016416 A CN200880016416 A CN 200880016416A CN 101678322 B CN101678322 B CN 101678322B
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- aluminium oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title abstract description 25
- 230000008569 process Effects 0.000 title abstract description 9
- 238000000746 purification Methods 0.000 title abstract 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 270
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 125
- 239000002245 particle Substances 0.000 claims abstract description 69
- 239000000243 solution Substances 0.000 claims abstract description 14
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 100
- 239000010936 titanium Substances 0.000 claims description 45
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 32
- 229910052719 titanium Inorganic materials 0.000 claims description 32
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000013459 approach Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 231100000572 poisoning Toxicity 0.000 abstract description 8
- 230000000607 poisoning effect Effects 0.000 abstract description 8
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- -1 ammonium ions Chemical class 0.000 abstract description 2
- 239000003637 basic solution Substances 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 21
- 230000009467 reduction Effects 0.000 description 18
- 150000002500 ions Chemical class 0.000 description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 16
- 239000011859 microparticle Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 239000002574 poison Substances 0.000 description 14
- 231100000614 poison Toxicity 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 238000003860 storage Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 238000001069 Raman spectroscopy Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 239000000446 fuel Substances 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910000420 cerium oxide Inorganic materials 0.000 description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 6
- 230000003334 potential effect Effects 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NDHFYDKYYXSPFR-UHFFFAOYSA-N CC(C)CO[Ti] Chemical compound CC(C)CO[Ti] NDHFYDKYYXSPFR-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- DCRIQAAPAFMPKP-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Al+3].[Ti+4] DCRIQAAPAFMPKP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910018967 Pt—Rh Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000892 gravimetry Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0211—Impregnation using a colloidal suspension
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0242—Coating followed by impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2255/209—Other metals
- B01D2255/2092—Aluminium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
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- Combustion & Propulsion (AREA)
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- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
A process for producing a catalyst support for exhaust gas purification; and a catalyst support for exhaust gas purification. The catalyst support such as alumina is prevented from being reduced in heat resistance by the presence of titania and has the function of inhibiting sulfur poisoning due to the titania. The process for producing a catalyst support for exhaust gas purification is characterized by including a treatment in which ammonium ions are adsorbed onto alumina particles in a basic solution and then the resultant alumina particles are brought into contact with a titania sol to thereby adsorb titania particles onto the alumina particles. The catalyst support for exhaust gas purification comprises alumina particles and titania particles adsorbed at least on basic sites in the surface of the alumina particles, and causes no increase in pH when immersed in an ammonium nitrate solution.
Description
Technical field
The present invention relates to be manufactured on and suppress to possess when hear resistance reduces S the poison method and the exhaust gas purifying catalyst carrier of inhibiting exhaust gas purifying catalyst carrier.
Background technology
Lean-combustion engine is a characteristic with low oil consumption, yet utilizes common three-way catalyst NOx to be purified in air-fuel ratio scope (under the oxygen excess atmosphere).The NOx that can realize rare air-fuel ratio scope with the NOx storage and reduction type catalyst of new cleaning principle exploitation purifies, and is on common three-way catalyst, to keep material (occlusion/sorbing material) as NOx and the catalyst that added alkali metal, alkaline-earth metal etc.NOx is become NO by the excess oxygen oxidation on the catalyst noble metal when the common running of air-fuel ratio
2, it remains on NOx as nitrate etc. and keeps on the material.After this, through be made as air-fuel ratio dense (the superfluous atmosphere of fuel) with the utmost point short time, nitrate etc. will be by CO, HC reduction, as N on the catalyst noble metal
2Be cleaned, discharge.
The manufacturing of NOx storage and reduction type catalyst is through on base materials such as cordierite, forming catalyst support layer (coat) such as aluminium oxide, makes it to support NOx maintenance materials such as catalyst noble metal such as Pt and K and carries out.In general, peculiar S poisons in the NOx storage and reduction type catalyst in order to suppress, and catalyst support layer is at aluminium oxide (Al
2O
3), zirconia (ZrO
2), cerium oxide (CeO
2) wait and add titanium oxide (TiO in the porous carrier particle
2) and form.Through the existence of titanium oxide, under the dense atmosphere of high temperature, carry out S and poison when regenerating, keep the disengaging of the SOx that material kept to obtain promoting by NOx.But,, have the problem that the hear resistance of catalyst reduces significantly because of the interpolation of titanium oxide.
In WO00/00283, disclose the NOx storage and reduction type catalyst that has used by titanium oxide and supported the carrier that the zirconia of Rh constitutes in advance.Utilize titanium oxide to suppress S and poison, through at ZrO
2On support Rh and improve detergent power.But, because the hear resistance of titanium oxide is low, therefore be all clinkerings easily of titanium oxide itself or catalyst noble metal, the detergent power that can't obtain to be expected improves.
In TOHKEMY 2001-9279 communique, disclose the NOx storage and reduction type catalyst that has used the carrier that the surface of aluminium oxide particles is covered with the Titanium particles below the particle diameter 10nm.In addition, as its manufacturing approach, disclose following method, that is, the pH that makes the slip that is made up of aluminium oxide particles and titanium oxide sol is less than 5, thereafter through pH is risen, and the aluminium oxide particles surface covered with titanium oxide microparticle.But in the manufacturing approach of TOHKEMY 2001-9279 communique, shown in Figure 10 like TOHKEMY 2001-9279 communique because titanium oxide sol can pass through isoelectric point in the pH uphill process, therefore can be condensed and thickization immediately at this time point.Under the pH at this moment, aluminium oxide is charged, thereby can not condense with titanium oxide sol.If further raise pH, then the titanium oxide sol condensation product just begins electronegative.But owing to need the longer time with condensed phase than dispersions again, so Titanium particles will be adsorbed on the aluminium oxide particles keeping condensing under the state of thickization.Like this, in the manufacturing approach of TOHKEMY 2001-9279 communique, not the state of titanium oxide microparticle probably with the surface coverage of aluminium oxide particles, but the state that aluminium oxide particles and the Titanium particles that has condensed mix simply.
In TOHKEMY 2004-321847 communique, disclose to have used on the aluminium oxide-titanium oxide composite oxides made from coprecipitation and support the NOx storage and reduction type catalyst that precursors of titanium oxide is burnt till the carrier that forms.But,, therefore can't obtain sufficient hear resistance because the hear resistance of titanium oxide is low.
In addition, in three-way catalyst, also exist S on catalyst carrier, to adhere to, by following H that generates such as the idling conditions after running at high speed as sulfate
2The problem of the foul smell due to the S.
Like this, when in catalyst carrier, adding titanium oxide, the hear resistance of comparing catalyst with the situation of not adding titanium oxide reduces, and therefore adds the S that brings by titanium oxide and poisons and suppress the problem of the original detergent power of effect and catalyst with regard to having to take into account.
Summary of the invention
The objective of the invention is to; The manufacturing approach and the exhaust gas purifying catalyst carrier of exhaust gas purifying catalyst carrier are provided; Its hear resistance that can prevent the catalyst carriers such as aluminium oxide that the existence by titanium oxide causes reduces, and possesses the S poisoning inhibitory action based on titanium oxide.
In order to reach above-mentioned purpose,, a kind of manufacturing approach of exhaust gas purifying catalyst carrier is provided according to the present invention; It is characterized in that; Comprise following processing, that is, and in alkaline solution; After making ammonium ion be adsorbed on the aluminium oxide particles, Titanium particles is adsorbed on this aluminium oxide particles through titanium oxide sol is contacted with this aluminium oxide particles.
In addition, according to the present invention, a kind of exhaust gas purifying catalyst carrier is provided, it is adsorbed with Titanium particles at the basic site on aluminium oxide particles surface at least, does not produce pH in the time of in impregnated in ammonium nitrate solution and rises.
Form the fine Titanium particles of colloidal sol through absorption on the aluminium oxide particles that has adsorbed ammonium ion; Carrier framework structure as aluminium oxide is changed; And the hear resistance of the Titanium particles on the aluminium oxide also improves; Therefore as generally hear resistance raising of catalyst, can bring into play high catalytic capability.
Description of drawings
Fig. 1 is the flow chart of expression based on the manufacturing process of the catalyst carrier of embodiments of the invention 1.
Fig. 2 is the curve map of expression by the variation of the zeta potential of activated alumina due to the coexistence of ammonium ion and titanium oxide sol.
Fig. 3 is the Raman analysis figure of embodiments of the invention 1.
Fig. 4 is the Raman analysis figure of embodiments of the invention 2.
Fig. 5 is the Raman analysis figure of the comparative example 3 of embodiments of the invention 3 and prior art.
Fig. 6 is that expression is for embodiments of the invention 4 and the duplicate curve map that the pH after the input changes in ammonium nitrate solution respectively.
The specific embodiment
The inventor infers, and then generally the hear resistance reason that will reduce is following as carrier in the high aluminium oxide of original hear resistance etc., to add titanium oxide.
The prior art of WO00/00283 has carried out using as the Ti source solution reaction of Ti ion (sulfate etc.), Ti organic metal (alkoxide) etc. in order to form titanium oxide.When high-fire resistance particles such as these Ti sources and aluminium oxide are combined; Ti for example gets between the particle of one-level particle or secondary particle of aluminium oxide with the form of ion; This part breaks away from the composition of aluminium oxide, becomes aluminium oxide titanium oxide composite oxides, so hear resistance reduces; Particle is reset easily, has caused the carrier surface area under the high temperature to reduce.Because of carrier surface area reduces, also can cause the catalyst noble metal that is supported, the cohesion that NOx keeps material, catalytic performance reduces significantly.
The present invention is based on above-mentioned investigation; Through Ti is not contacted with high-fire resistance particles such as aluminium oxide with the form of organo-metallic compounds such as ion or complex ion, alkoxide; And titanium oxide sol is contacted with aluminium oxide; Just be adsorbed on the aluminium oxide particles from beginning at first, do not show above-mentioned hear resistance degradation mechanism, thereby guarantee hear resistance as carrier as Titanium particles.
But, merely in the titanium oxide sol aqueous solution, adding activated alumina, the titanium oxide microparticle that forms colloidal sol also is to be adsorbed on the active oxidation aluminum particulate micro-ly.This is because titanium oxide sol has the isoelectric point near neutrality with to burn till titanium oxide different, is difficult to the aluminium oxide generation current potential property absorption similar with charged characteristic.
In addition; Shown in TOHKEMY 2001-9279 communique; For method from acidic side rising pH; In the pH uphill process, through isoelectric point the time, can cause cohesion/thickization of titanium oxide sol as previously mentioned inevitably, the Titanium particles that the cohesion that causes thus/thick has been changed becomes the state that mixes simply with aluminium oxide particles.
Among the present invention, in alkaline solution, make ammonium ion (NH
4 +) be adsorbed on the aluminium oxide particles, and the titanium oxide microparticle that forms colloidal sol is adsorbed on this aluminium oxide particles.According to following mechanism, this can realize.
That is, even alkaline oxygenated titanium colloidal sol, charged characteristic is also approximate with aluminium oxide.But, NH
4 +Ion is different fully with adsorptivity on aluminium oxide to the adsorptivity on the titanium oxide sol.NH can take place on aluminium oxide
4 +The absorption of ion is if increase NH
4 +Ion concentration, then the negative electrical charge of aluminium oxide will reduce.Because of Superhydrophilic OH
-The big titanium oxide of absorption affinity on NH can not take place then
4 +The absorption of ion is even increase NH
4 +Ion concentration, negative electric charge does not reduce yet.That is, can think, in aluminium oxide at surface adsorption NH
4 +Ion, top layer become positive charge partly, thereby can adsorb electronegative titanium oxide sol.
Because the part on top layer becomes positive charge and only occurs on the aluminium oxide; On titanium oxide, still keep negative electrical charge, therefore can infer, the absorption of current potential property just occurs between aluminium oxide and the titanium oxide; No matter be between the aluminium oxide, or titanium oxide between, the absorption of current potential property can not take place.
Like this just can be implemented in the state that has adsorbed titanium oxide microparticle on the aluminium oxide particles of high-fire resistance first.Say typically, can think that aluminium oxide particles is the above secondary particle of tens of nm that the one-level particle coacervation below the 10nm forms, and on its surface, is adsorbing the one-level particle of the titanium oxide about the 10nm that has formed colloidal sol.
After the aluminium oxide filtration that is adsorbed with titanium oxide microparticle that will so obtain, washing, drying,, just can obtain the catalyst carrier that constitutes by the aluminium oxide that has supported titanium oxide microparticle through burning till.The cohesion of the aluminium oxide that at this sintering process or when heat-resisting the cohesion of titanium oxide can take place in the past and accompany with it, catalytic capability reduces significantly.
Relative with it; Catalyst carrier of the present invention has been adsorbed the structure of titanium oxide microparticle on the aluminium oxide skeleton highly stable; Be when burning till or when heat-resisting, can not condense; The aluminium oxide skeleton has been kept the high surface state at initial stage, in addition, has also kept the graininess that derives from colloidal sol by the titanium oxide that its absorption supports.
Basic site is arranged on aluminium oxide particles,, therefore become the reason that causes S to poison because basic site has the character of absorption sulphur.Among the present invention,, can prevent that therefore (or alleviating) S poisons owing to fine Titanium particles combines to shelter with the basic site of alumina surface.Relative with it, in the prior art, owing to Titanium particles cohesion/thickization is difficult to combine with basic site, thus S poison prevent that effect is little.
Whether the basic site of aluminium oxide is sheltered for titanium oxide, can be utilized to impregnated in ammonium nitrate (NH
4NO
3) pH in the solution time rises and judge.That is, on the basic site of aluminium oxide, be combined with titanium oxide (TiO
2) situation under, even impregnated in NH
4NO
3In the solution, NH
4 +Ion and NO
3 -Ion to the absorption on the aluminium oxide also very a little less than, pH can not change in fact.Relative with it, on the basic site of aluminium oxide, do not combine titanium oxide (TiO
2) situation under, on the basic site of aluminium oxide, will partly adsorb NO
3 -Ion.Like this, because the OH that coordination originally
-Ion is broken away from release, so pH rises.Like this, if there is not pH variation or few, then can judge has by sheltering due to the titanium oxide, if there is pH to rise, then can judge not by sheltering due to the titanium oxide.
Among the present invention, the basic site of aluminium oxide particles is sheltered with titanium oxide microparticle, just can be prevented effectively that S poisons through using titanium oxide sol.
And catalyst carrier of the present invention can adopt following formation, that is, be main body with the aluminium oxide as framework ingredient, as required to wherein adding other framework ingredient such as zirconia, cerium oxide.This kind framework ingredient for example is activated alumina, zirconia oxide, cerium oxide composite oxides of high surface etc.In addition, also can use the activated alumina that is added with terres rares that in framework ingredient, added NOx and kept material, be added with the activated alumina of Ba etc.
Used the NOx storage and reduction type catalyst of catalyst carrier of the present invention can utilize method in the past to make.Promptly; Say that typically (1) is coated with the slip that is made up of catalyst carrier of the present invention on base materials such as cordierite, dry, burn till and form catalyst support layer (coat); (2) on this coat; Dipping, the drying of utilization in the solution of catalyst noble metals such as Pt, Rh, Pd, burn till and after having supported the catalyst noble metal, (3) utilize again to NOx such as alkali metal, alkaline-earth metal, rare earth metal keep in the solution of material dipping, drying, burn till, support NOx and keep material.
Embodiment
[embodiment 1]
Utilize the present invention, make catalyst carrier according to following Step By Condition.
(1) making of titanium oxide sol
Utilize disclosed method in the japanese kokai publication hei 7-232925 communique; Promptly; Utilization make titanium dioxide powder aqueous phase contacting with cation exchange column in the presence of the acid or in the presence of alkali with method that anion exchanger contacts in the latter's method, make alkaline oxygenated titanium colloidal sol.Used titanium oxide sol is that commercially available catalyst changes into system, particle diameter: 10nm, crystal structure: anatase structures, colloidal sol is with TiO
2The meter dilution is 5wt%, and pH is adjusted into pH10.
(2) absorption on activated alumina
The titanium oxide sol that utilizes aforesaid operations to make is adsorbed on the activated alumina with the step shown in the flow chart shown in Figure 1.
Here, make Ti/Al=5/100 (atomic ratio).
At first, preparation 0.05mol/L ammonium nitrate+ammoniacal liquor, pH are made as 10 the 5L aqueous solution.To wherein adding dried active aluminium oxide (WR Grace system) 1kg, stir, carry out the degassing of powder pore.After about 30 minutes, add the alkaline oxygenated titanium colloidal sol of above-mentioned dilution 1567g at leisure, added all with about 5 minutes and measure.Continue stir 1h thereafter.Filter, carry out 1 washing, carry out a night 120 ℃ drying.Then, burn till 2h at 800 ℃.Based on the weight after burning till, can confirm that titanium oxide sol is all supported basically.
Though used alkaline oxygenated titanium colloidal sol in the present embodiment, yet also can use acidic oxidation titanium colloidal sol.Under this situation, utilize following pre-treatment to become alkalescence.That is, in 0.3mol/L ammoniacal liquor 800ml, add the acidic oxidation titanium colloidal sol of the 10wt% of 500g, with ammoniacal liquor pH is adjusted to 10 then, continue to stir at least more than the 2h.After utilizing this operation to implement pre-treatment, carry out the processing identical with the situation of above-mentioned alkaline colloidal sol.
[comparative example 1]
With drying activated alumina add in the distilled water, after the stirring, filter gravimetry and obtain water absorption rate.Then, prepare the isobutoxy titanium ethanolic solution get ready in advance.According to making its concentration reach the mode of Ti/Al=5/100 (atomic ratio) based on above-mentioned water absorption rate, suction isobutoxy titanium ethanolic solution in dry alumina powder.Filter, after 80 ℃ of dryings, burn till 2h at 800 ℃ thereafter.
[comparative example 2]
Prepare common titanium oxide sol (the former industry system of stone),, make it to reach the degree that to flood the dry aluminium oxide that is added to wherein adding a spot of water.After stirring 1h, heating, transpiring moisture at leisure.Also continue heating after can't stirring becoming, behind the bone dry, burn till 2h at 800 ℃.
In the comparative example 2, even in the titanium oxide sol aqueous solution, add activated alumina and stir, titanium oxide sol also just is adsorbed on the activated alumina pettiness very much.This is because titanium oxide sol has the isoelectric point near neutrality with to burn till titanium oxide different, is difficult to the aluminium oxide generation current potential property absorption similar with charged characteristic.So, heats in order to ensure loading, concentrates, dry, yet most Titanium particles condenses between Titanium particles.
Relative with it, in the embodiments of the invention 1, as before illustrated, utilize NH
4 +Be adsorbed on the aluminium oxide easily, be difficult to be adsorbed on the adsorptive selectivity on the titanium oxide sol, the aluminium oxide top layer becomes positive charge partly, and negative electrical charge is kept on the titanium oxide sol top layer, thus titanium oxide sol just by current potential property be adsorbed onto on the aluminium oxide.At this moment, current potential property absorption between the aluminium oxide, between the titanium oxide can not take place.The titanium oxide that consequently, can obtain to derive from the graininess of colloidal sol is adsorbed onto the state on the aluminium oxide skeleton.
As an example, in Fig. 2,, relatively represented by NH to activated alumina and titanium oxide sol
4 +The variation of the zeta potential that the coexistence of ion causes.In mensuration, used and in distilled water, disperseed to carry out the also material of stabilisation 1h of pH adjustment behind colloidal sol or the carrier.
As shown in the figure, activated alumina is because of NH
4 +The coexistence of ion and negative zeta potential is reduced significantly, relative therewith, the current potential of titanium oxide sol is not because of NH
4 +The coexistence of ion and any substantial variation is arranged can see that potential difference between the two produces evident difference.This be because, as stated, NH
4 +Be adsorbed on the activated alumina ion selectivity, be adsorbed on the activated alumina through this potential difference titanium oxide sol.
< surface area of carrier >
The surface area of the catalyst carrier of making in utilized determination of nitrogen adsorption embodiment 1, comparative example 1, the comparative example 2.To measure the result is shown in the table 2.And, for relatively, also put down in writing in the lump as the titanium dioxide powder (initial stage anatase titanium dioxide) of raw material use and the surface area of activated alumina.
The surface area of table 1 carrier (800 ℃, when burning till 2h)
| Classification | Kind of carrier | Surface area (m 2/g) |
| Titanium oxide (initial stage anatase titanium dioxide) | 22.1 | |
| Comparative example 1 | Support Ti alkoxide ※ on the activated alumina | 123.0 |
| Comparative example 2 | Solid ※ is done in activated alumina+acidic oxidation titanium colloidal sol evaporation | 160.4 |
| |
Activated alumina+titanium oxide sol absorption ※ | 165.2 |
| Activated alumina | 180.5 |
※: Ti/Al mol ratio=5/100
The catalyst carrier of embodiment 1 is minimum with respect to the reduction of the surface area of activated alumina.Relative with it, added with the reduction of the surface area of the catalyst carrier of the comparative example 1 of the Ti of embodiment 1 same amount very big.Though the reduction of comparative example 2 surface areas is few, yet as follows, HC modification ability reduces.
< steam modified-reaction >
Titanium oxide is effectively for the activate of hydrocarbon, can think that following steam modified-reaction is by high speed.
CmHn+mH
2O→mCO+(2m+n)/2·H
2
Hydrogen that utilization is generated and the strong reducing action of CO can promote to have taken place as sulfate the reduction/disengaging of the S composition of poisoning.
Use the catalyst carrier of embodiment 1, comparative example 1, comparative example 2, utilize following step to make NOx storage and reduction type catalyst.Wherein, For embodiment 1; Made the application examples 1 of in the catalyst carrier of embodiment 1 is formed, having added zirconia oxidation titanium composite oxide, in addition, made the application examples 2 that has increased NOx maintenance amount of substance corresponding to comparing than application examples 1 big surface area and with embodiment 1.In addition, also made the catalyst of the catalyst carrier of using the prior art example.
< making step of NOx storage and reduction type catalyst >
400cell/in to 2L
2Monolith substrate on utilize cladding process impregnated carrier slip, dry, burn till.On it, utilize known impregnation method absorption to support Pt-Rh.Then make the aqueous solution of carrier absorption Ba and alkali-metal salt as the NOx occlusion material, dry, burn till and process catalyst.
To each NOx storage and reduction type catalyst, the superfluous HC when utilizing following condition to measure dense pulse (richpulse) is to the conversion ratio of CO.
< condition determination of HC/CO conversion ratio >
The steam modification ability of HC is to utilize from rare air-fuel ratio running to switch 5 seconds average HC+H to dense air-fuel ratio running
2O → CO+H
2Reaction try to achieve.In rare air-fuel ratio running, be made as the gas that is equivalent to A/F=21, in dense air-fuel ratio running, be made as the gas that is equivalent to A/F=14.
To be shown in the table 2 in the mensuration result set to each catalyst carrier.
Table 2
Result according to table 2 can know clearly that the application examples 1,2 of embodiment 1 is compared with comparative example 1,2 and prior art example, improves significantly to the conversion ratio of CO.
In addition, in table 2, also show the NOx purifying rate of [behind the thermal endurance] and " thermal endurance+S poisons after the regeneration " in the lump.The condition of thermal endurance and S poisoning regeneration is as follows.
< condition of thermal endurance >
Thermal endurance is under 750 ℃, to carry out the 20h air to burn till.
< condition that S poisons and regenerates >
S poisoning test is that every 1L catalyst utilizes SO
2The gas of gas+be equivalent to A/F=21 makes it to poison.S is made as with S through amount and counts 24g/L-cat.The regeneration condition that S poisons is to carry out 30 seconds with the gas that is equivalent to A/F=14 down at 600 ℃, and switching to the gas that is equivalent to A/F=21 carried out 10 seconds, and such operation was carried out 10 minutes repeatedly.
As shown in table 2, the application examples 1,2 of embodiment 1 is all increasing substantially aspect NOx reproducibility and the S disengaging property with respect to comparative example 1,2 and prior art example.
< Raman analysis >
Because embodiment 1 has very high catalytic activity as stated, the titanium oxide (TiO that therefore supports for research institute
2) form of particle, carried out Raman analysis.The result is shown among Fig. 3.
According to opinion in the past, titanium oxide near than 600 ℃ under the higher temperature crystal structure become rutile structure from anatase structures, with it together because of thickization of cohesion (hear resistance reduction).
Relative with it, in the embodiments of the invention 1,, yet still keep the titanium oxide of anatase structures although 800 ℃ of burning till of carrying out 2h.That is, the peak that indicates A among the figure is the peak of anatase structures, and the very wide expression particle in peak is a particulate.Like this according to the method for the invention, the absorption of titanium oxide on aluminium oxide takes place fully, and the hear resistance reduction of aluminium oxide does not take place yet.Can confirm like this, still keep highly active anatase structures with graininess at the Titanium particles that absorption supports under the state on the aluminium oxide.
[embodiment 2]
On the catalyst carrier of the present invention of in embodiment 1, making, utilize impregnation to support the Pt of 1wt%, make three-way catalyst (it being called " aluminium oxide catalyst that is adsorbed with the Pt/ titanium oxide microparticle ").
As relatively, on commercially available cerium oxide zirconia catalyst carrier (Ce is 40at% with respect to whole metals [Ce+Zr]), utilize impregnation to support the Pt of 1wt%, make three-way catalyst (it being called " Pt/ cerium oxide zirconia catalyst ").
To each three-way catalyst of made, circulation SO
2100ppm, O
25% flow model gas 3h has carried out the S poisoning experiment.
Among Fig. 4, be illustrated in the result who carries out Raman analysis behind the S poisoning experiment.
As shown in the drawing, for Pt/ cerium oxide zirconia catalyst relatively, can see SO significantly
3Absorption, relative therewith, for the aluminium oxide catalyst that is adsorbed with the Pt/ titanium oxide microparticle that on the catalyst carrier of embodiment 1, has supported Pt, do not see SO basically
3Absorption.
[embodiment 3]
The catalyst carrier that the method for utilizing method of the present invention and TOHKEMY 2001-9279 communique is obtained compares.
At first, utilize the present invention, made catalyst carrier according to following Step By Condition.
(1) making of titanium oxide sol
After titanium sulfate aqueous solution is separated with ammoniacal liquor, become neutrality with nitric acid, thereby made acidic oxidation titanium colloidal sol.Used titanium oxide sol is the commercially available former industry system STS-100 of stone, cohesion particle diameter 15nm, impalpable structure, and colloidal sol is with TiO
2The meter dilution is adjusted into 10 for 5wt% with pH, in order to realize the dispersion again of titanium oxide sol, stirs at least 2 hours.
(2) absorption on activated alumina
The acidic oxidation titanium colloidal sol that utilizes aforesaid operations to make is accordinged to be adsorbed on the activated alumina with embodiment 1 identical step.But, after filtration that utilizes centrifugation and washing, 80 ℃ of following dry nights.At 800 ℃ burn till 2h thereafter.Based on the weight after burning till, can confirm that titanium oxide sol is all supported basically.
[comparative example 3]
Then, the embodiment 1 according to TOHKEMY 2001-9279 communique has made catalyst carrier.Wherein, used titanium oxide sol is same as described above, according to making the mode of Ti/Al=5/100 (atomic ratio) carry out the raw material cooperation.
That is, in pH being adjusted into 2 ion exchange water with nitric acid, adding activated alumina and titanium oxide sol and mix while stir.In the slip of gained, pH is made as 7 while stir dropping ammonia.Thereafter, after filtration that utilizes centrifugation and washing, 80 ℃ of one nights of drying.At 800 ℃ burn till 2h thereafter.
To the catalyst carrier of making respectively in embodiment 3 and the comparative example 3, carried out utilizing the surface area test and the Raman analysis of nitrogen adsorption method.
< surface area of carrier >
The mensuration result of surface area is shown in the table 3.And, for relatively, also charged to the surface area that is merely activated alumina before the adsorption and oxidation titanium in the lump.
The surface area of table 3 carrier (800 ℃, when burning till 2h)
| Classification | Kind of carrier | Surface area (m 2/g) |
| Activated alumina | 195.2 | |
| Embodiment 3 | Activated alumina+titanium oxide sol absorption (* 2) | 190.1 |
| Comparative example 3 | Activated alumina+titanium oxide sol absorption (* 2) (* 3) | 175.9 |
*2: acidic oxidation titanium colloidal sol (amorphous), Ti/Al mol ratio=5/100
*3: the condition (pH rises to pH7 from pH5) of the embodiment 1 of TOHKEMY 2001-9279 communique
As shown in table 3; Heating through 800 ℃ * 2h; Compare before adopting carrier and the heating of embodiment 3 of method of the present invention, surface area does not reduce basically, and is relative with it; Compare before adopting carrier and the heating of comparative example 3 of method of TOHKEMY 2001-9279 communique, surface area reduces significantly.
< Raman analysis result >
The Raman analysis result who has represented 800 ℃ of each catalyst carriers after burning till among Fig. 5.Shown in A among the figure, the catalyst carrier that adopts comparative example 3 (TOHKEMY 2001-9279 communique) can be seen the anatase titanium dioxide peak as putting down in writing in the TOHKEMY 2001-9279 communique.Its peak intensity is very strong, and expression is the thick anatase type titanium oxide crystal of having changed.That is,, lost the impalpable structure at initial stage, be changed to the anatase titanium dioxide crystal for the method for comparative example 3 (TOHKEMY 2001-9279 communique).
Relative with it, adopt the catalyst carrier of embodiments of the invention 3 to can't see the peak fully, even at 800 ℃ of impalpable structures of also keeping the initial stage after burning till.This can infer be because, among the present invention, because fine Titanium particles combines with aluminium oxide particles securely; Therefore aluminium oxide particles has also been kept impalpable structure in 800 ℃ are burnt till; Relative therewith, for the method for comparative example 3 (TOHKEMY 2001-9279 communique), Titanium particles condenses and thickization; A little less than the combining of most Titanium particles and aluminium oxide particles, therefore aluminium oxide particles clinkering and crystallization in 800 ℃ are burnt till.
[embodiment 4]
Carried out being used to confirm the experiment of Titanium particles to the masking effect of aluminium oxide particles basic site.
< preparation of sample >
Utilize the Step By Condition identical, carry out the making of titanium oxide sol and the absorption on activated alumina, made the alumina catalyst carrier that is adsorbed with titanium oxide microparticle with embodiment 1.
For relatively, also prepared to be merely the sample of active oxidation aluminum particulate.
< experiment >
Utilize distilled water to process ammonium nitrate solution with concentration 0.15mol/L, then pH is 5.6.Measured to the sample of the above-mentioned alumina catalyst carrier that is adsorbed with titanium oxide microparticle that wherein drops into 25g/100mL respectively and the pH after being merely the sample of activated alumina.The result is shown among Fig. 6.
As shown in the figure, drop under the situation that adopts the alumina catalyst carrier that is adsorbed with titanium oxide microparticle of the present invention, the pH of ammonium nitrate solution does not change in fact.Relative with it, under the situation that only drops into activated alumina, pH rises to 8.0.Its reason can be thought as follows.
Adopt the alumina catalyst carrier that is adsorbed with titanium oxide microparticle of the present invention, owing to be combined with titanium oxide (TiO at the basic site of aluminium oxide
2), even therefore be impregnated into NH
4NO
3In the solution, NH
4 +Ion and NO
3 -Ion to the absorption on the aluminium oxide also very a little less than, pH can not change in fact.
Relative with it, be merely the sample of aluminium oxide owing on the basic site of aluminium oxide, do not combine titanium oxide (TiO
2), therefore on the basic site of aluminium oxide, be adsorbed with NO partly
3 -Ion.Like this, because the OH of original institute coordination
-The ion disengaging is released, so pH rises.
Like this, if there is not substantial pH to change, then can judge has by sheltering due to the titanium oxide, if there is pH to rise, then can judge not by sheltering due to the titanium oxide.
According to the present invention, through using titanium oxide sol the basic site of aluminium oxide particles is sheltered with titanium oxide microparticle, can prevent effectively that S poisons.
Utilize possibility in the industry
According to the present invention; A kind of manufacturing approach of NOx storage and reduction type catalyst can be provided; Can prevent that the hear resistance that the existence by titanium oxide causes from reducing, and has the S poisoning inhibitory action based on titanium oxide, raising effect of modification ability and the original hear resistance of catalyst of HC concurrently.
On the other hand, S also can be attached on the catalyst carrier as sulfate in three-way catalyst, and the idling condition after running at high speed etc. are down by generating H
2The foul smell that S causes is a problem, yet if use carrier of the present invention, can suppress significantly adhering to of sulfate, can obtain not produce basically the excellent effect of foul smell.
Claims (2)
1. the manufacturing approach of an exhaust gas purifying catalyst carrier; It is characterized in that; Comprise following processing, that is, and in alkaline solution; After making ammonium ion be adsorbed on the aluminium oxide particles, Titanium particles is adsorbed on the said aluminium oxide particles through titanium oxide sol is contacted with said aluminium oxide particles.
2. an exhaust gas purifying catalyst carrier that obtains through the described manufacturing approach of claim 1 is adsorbed with Titanium particles at the surperficial basic site of aluminium oxide particles at least, does not produce pH in the time of in impregnated in ammonium nitrate solution and rises.
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| JP2007169176 | 2007-06-27 | ||
| JP169176/2007 | 2007-06-27 | ||
| PCT/JP2008/061934 WO2009001962A1 (en) | 2007-06-27 | 2008-06-25 | Process for producing catalyst support for exhaust gas purification and catalyst support for exhaust gas purification |
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| CN101678322A CN101678322A (en) | 2010-03-24 |
| CN101678322B true CN101678322B (en) | 2012-10-03 |
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|---|---|
| US (1) | US8034743B2 (en) |
| EP (1) | EP2172265B1 (en) |
| JP (1) | JP5327048B2 (en) |
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| CN101918135A (en) * | 2009-03-18 | 2010-12-15 | 丰田自动车株式会社 | Nanoparticle loading method |
| JP5932650B2 (en) * | 2009-10-08 | 2016-06-08 | ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット | Sulfur resistant alumina catalyst support |
| CN103861658B (en) * | 2014-02-28 | 2015-12-02 | 中国海洋石油总公司 | A kind of preparation method of spherical titania-alumina mixed oxide |
| CN104353503B (en) * | 2014-11-12 | 2016-05-18 | 中国海洋石油总公司 | A kind of preparation method of spherical sial complex carrier |
| CN104353504B (en) * | 2014-11-12 | 2016-05-18 | 中国海洋石油总公司 | A kind of preparation method of spherical titanium aluminium complex carrier |
| JP6390492B2 (en) * | 2015-03-30 | 2018-09-19 | 株式会社Ｓｏｋｅｎ | NOx purification system controller and reducing agent addition system |
| US10562017B2 (en) * | 2017-01-05 | 2020-02-18 | GM Global Technology Operations LLC | Ion adsorption of oxide layers to hinder catalyst sintering |
| US10376872B2 (en) | 2017-01-05 | 2019-08-13 | GM Global Technology Operations LLC | Solution-based approach to make porous coatings for sinter-resistant catalysts |
| US10596563B2 (en) | 2017-01-27 | 2020-03-24 | GM Global Technology Operations LLC | Sinter-resistant stable catalyst systems by trapping of mobile platinum group metal (PGM) catalyst species |
| KR102310675B1 (en) * | 2018-08-20 | 2021-10-12 | (주)엘엑스하우시스 | Exhaust gas purifying catalyst |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3928236A (en) * | 1974-11-25 | 1975-12-23 | Kaiser Aluminium Chem Corp | Alumina catalyst carriers and the process for producing them |
| JPH0628719B2 (en) * | 1990-06-13 | 1994-04-20 | 工業技術院長 | Method of coating fine particle surface |
| JPH0628719A (en) | 1992-07-08 | 1994-02-04 | Ricoh Co Ltd | Development processor |
| JP3821521B2 (en) * | 1996-10-22 | 2006-09-13 | 触媒化成工業株式会社 | Titania-alumina support, process for producing the same, and hydrotreating catalyst using the same |
| DE69923843T2 (en) * | 1998-06-30 | 2006-04-06 | Toyota Jidosha K.K., Toyota | METHOD AND CATALYST FOR CLEANING EXHAUST GAS AND METHOD FOR PRODUCING THE CATALYST |
| US6251823B1 (en) * | 1998-08-12 | 2001-06-26 | Sumitomo Metal Mining Co., Ltd. | Production of spherical catalyst carrier |
| JP4240250B2 (en) * | 1999-06-29 | 2009-03-18 | 株式会社豊田中央研究所 | Exhaust gas purification catalyst, method for producing the same, and exhaust gas purification method |
| JP3781417B2 (en) * | 2002-06-28 | 2006-05-31 | 千代田化工建設株式会社 | Porous titanium oxide carrier, catalyst using the same, and method for producing porous titanium oxide carrier |
| JP4171977B2 (en) | 2003-04-21 | 2008-10-29 | 株式会社豊田中央研究所 | Catalyst carrier, production method thereof, catalyst, and exhaust gas purification method |
| JP3827313B2 (en) * | 2003-05-07 | 2006-09-27 | エヌ・イーケムキャット株式会社 | Method for producing titania-coated alumina particles |
| DE10352816A1 (en) * | 2003-11-12 | 2005-06-09 | Sachtleben Chemie Gmbh | Process for the preparation of a high-temperature stable, TiO 2 -containing catalyst or catalyst support |
| US7820583B2 (en) * | 2006-08-24 | 2010-10-26 | Millennium Inorganic Chemicals, Inc. | Nanocomposite particle and process of preparing the same |
-
2008
- 2008-06-25 CN CN2008800164165A patent/CN101678322B/en not_active Expired - Fee Related
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- 2008-06-25 JP JP2009520663A patent/JP5327048B2/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| JP特开2004-33819A 2004.02.05 |
| S. Sivakumar et al..Nanoporous titania–alumina mixed oxides—an alkoxide free sol–gel synthesis.《Materials Letters》.2004,第58卷2664– 2669. * |
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| US20100248957A1 (en) | 2010-09-30 |
| US8034743B2 (en) | 2011-10-11 |
| EP2172265B1 (en) | 2016-06-15 |
| CN101678322A (en) | 2010-03-24 |
| JPWO2009001962A1 (en) | 2010-08-26 |
| JP5327048B2 (en) | 2013-10-30 |
| EP2172265A4 (en) | 2011-06-22 |
| WO2009001962A1 (en) | 2008-12-31 |
| EP2172265A1 (en) | 2010-04-07 |
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